CN106478134A - The preparation method of high temperature resistant low temperature synthesis bulk spinelle aerogel material - Google Patents
The preparation method of high temperature resistant low temperature synthesis bulk spinelle aerogel material Download PDFInfo
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- CN106478134A CN106478134A CN201610885879.1A CN201610885879A CN106478134A CN 106478134 A CN106478134 A CN 106478134A CN 201610885879 A CN201610885879 A CN 201610885879A CN 106478134 A CN106478134 A CN 106478134A
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- 239000000463 material Substances 0.000 title claims abstract description 35
- 239000004964 aerogel Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 20
- 239000011777 magnesium Substances 0.000 claims abstract description 20
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000000352 supercritical drying Methods 0.000 claims abstract description 11
- 230000032683 aging Effects 0.000 claims abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- 230000007062 hydrolysis Effects 0.000 claims abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 7
- 150000002118 epoxides Chemical class 0.000 claims abstract 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- 238000010438 heat treatment Methods 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- 239000000499 gel Substances 0.000 claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 11
- 229910052596 spinel Inorganic materials 0.000 claims description 11
- 229910001051 Magnalium Inorganic materials 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000011029 spinel Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- ZATZOOLBPDMARD-UHFFFAOYSA-N magnesium;hydrate Chemical compound O.[Mg] ZATZOOLBPDMARD-UHFFFAOYSA-N 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 7
- 239000011240 wet gel Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- SWCIQHXIXUMHKA-UHFFFAOYSA-N aluminum;trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SWCIQHXIXUMHKA-UHFFFAOYSA-N 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- -1 magnesium aluminate Chemical class 0.000 claims description 4
- 238000010943 off-gassing Methods 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical group CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical group [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
- 235000013844 butane Nutrition 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 238000006073 displacement reaction Methods 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 150000004682 monohydrates Chemical class 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- 150000002921 oxetanes Chemical class 0.000 claims description 2
- 229960004424 carbon dioxide Drugs 0.000 claims 2
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 claims 2
- 229910002090 carbon oxide Inorganic materials 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000000701 coagulant Substances 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 6
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910001593 boehmite Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000002924 oxiranes Chemical class 0.000 description 3
- 239000011819 refractory material Substances 0.000 description 3
- 238000000518 rheometry Methods 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 239000004568 cement Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000011010 synthetic spinel Substances 0.000 description 2
- 208000035985 Body Odor Diseases 0.000 description 1
- 206010055000 Bromhidrosis Diseases 0.000 description 1
- 229910026161 MgAl2O4 Inorganic materials 0.000 description 1
- BZUCEGSPQJQDEQ-UHFFFAOYSA-N [O].CCCO Chemical compound [O].CCCO BZUCEGSPQJQDEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0045—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by a process involving the formation of a sol or a gel, e.g. sol-gel or precipitation processes
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/44—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminates
- C04B35/443—Magnesium aluminate spinel
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/624—Sol-gel processing
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- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
- C04B35/62655—Drying, e.g. freeze-drying, spray-drying, microwave or supercritical drying
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Abstract
The present invention relates to a kind of preparation method of high temperature resistant low temperature synthesis bulk spinelle aerogel material.By magnesium source and silicon source are mixed, after hydrolysis, introduce coagulant epoxide, obtain spinelle aerogel precursor body through collosol and gel, aging and supercritical drying, then carry out air forged burning under Muffle furnace, thus finally preparing a kind of block spinelle aerogel material of high temperature resistant low temperature synthesis.The present invention has the advantages that materials are simple and technique is simple and direct, and energy consumption is low simultaneously, and technical process is simple to operate, easily realizes large-scale production.
Description
Technical field
The invention belongs to the preparation technology field of aerogel material is and in particular to a kind of block point of high temperature resistant low temperature synthesis is brilliant
The preparation method of stone aerogel material.
Background technology
Magnesium aluminate spinel (MgAl2O4) it is a kind of oxide material possessing property, there is good anti-erosion, rotten
Erosion, peel-ability are strong, and slag resistance is good, abrasion resistance, good thermal shock stability, simultaneously but also with high temperature resistant, photocatalysis performance
The features such as excellent, excellent in optical properties, can be widely applied to photocatalysis, electrochemistry, refractory material, smelting iron and steel, cement return
The fields such as rotary kiln, rheology and chemical industry.Wherein, preparation high-purity, high chemical uniformity, granularity be equal, pore-size distribution is consistent
Spinel nano material has caused the great interest of scientific research personnel.Currently preparing spinel mainly has solid phase method and wet
Chemical method, wherein traditional solid phase method needs higher heat treatment temperature, longer response time, and energy consumption is higher, and brilliant
Particle size is easy to grow up.And wet chemical method mainly includes coprecipitation, spraying process, freeze-drying, hydro-thermal method, emulsion
Method, sol-gel process etc..Wherein, because reaction temperature is low, the material purity of preparation is high, specific surface area is big for sol-gel process,
Pore-size distribution is concentrated, and is therefore widely used.
Aeroge, as a kind of light porous material possessing three-D nano-porous structure, has low-density, high-ratio surface
The features such as long-pending, high porosity, possesses wide application prospect at aspects such as absorption, catalysis, heat-insulated and impedance coupler.If by point
Spinel is prepared into porous aerogel structure, it will the correlated performance of raising spinel further, such as heat resistance,
Specific surface area, pore-size distribution and photocatalysis performance.Currently it is related to spinelle mesoporous material and nanocrystalline research report, but
Not with regard to the pertinent literature of synthetic spinel aerogel material, therefore in this patent, supercritical is combined using sol-gal process
Drying process and heat treatment low temperature synthetic spinel aerogel material will be for this material in photocatalysis, electrochemistry, refractory material, steel
The application in the fields such as ferrum smelting, high-temperature gas filter, membrance separation, rheology chemical industry provides powerful material base.
Content of the invention
The invention aims to improving the deficiency of prior art presence and providing a kind of high temperature resistant low temperature synthesis block
The preparation method of spinelle aerogel material, the method materials and process is simple, structure-controllable, energy consumption is low, the airsetting prepared
Glue material possesses low-density, Gao Bibiao, antioxidation, the characteristic such as high temperature resistant, to realize aerogel material photocatalysis, electrochemistry,
The application in the fields such as refractory material, smelting iron and steel, cement rotary kiln, rheology and chemical industry possesses positive production meaning.
The technical scheme is that：The high temperature resistant high preparation method than table block shape spinelle aerogel material, it is concrete
Step is as follows：
(1), after magnesium source, silicon source, water, ethanol uniformly being mixed, after uniform stirring at a temperature of 20～50 DEG C, obtain water
The magnalium binary sol system of solution；
(2) epoxide is added in the binary sol system obtain in step (1), at a temperature of 20～40 DEG C all
Even stirring is poured into and is reacted in mould to gel, places 15～30h；
(3) Ageing solution will be added in step (2), enter line replacement 3～6 times in 30～60 DEG C of baking oven, every time 12～
24h；
(4) wet gel obtaining in step (3) is carried out supercritical drying process, obtain magnesium aluminate spinel aerogel precursor
Body；
(5) composite aerogel obtaining in step (4) is carried out air heat treatment under the air atmosphere of Muffle furnace, finally
Obtain spinelle aeroge；
Wherein：Magnesium source in step (1), silicon source, water, ethanol are according to 1：(1～4)：(70～120)：The rubbing of (15～45)
You mix than uniform；Epoxide in step (2) and magnesium source are according to mol ratio (8～16)：1 is mixed.
Silicon source described in preferred steps (1) is Aluminium chloride hexahydrate, ANN aluminium nitrate nonahydrate, aluminium secondary butylate or aluminum isopropylate.
One or more of.Magnesium source described in preferred steps (1) is Magnesium dichloride hexahydrate, nine nitric hydrate magnesium, two nitric hydrates
One or more of magnesium, bitter salt or monohydrate acid magnesium.
Epoxide described in preferred steps (2) is expoxy propane, cis -2,3 epoxy butanes, oxetanes or ring
One or more of oxygen propanol.
Mixing speed in preferred steps (1) is 400～600rpm, and mixing time is 0.5～4h；Stirring in step (2)
Mixing speed is 400～600rpm, and mixing time is 0.1～1h；Displacement number of times in step (2) is 3～6 times, when replacing every time
Between be 12～24h.
Ageing solution described in preferred steps (3) is one of ethanol, methanol, acetone, ether, n-amyl alcohol or isopropanol
Or it is several.
Drying meanss described in preferred steps (5) are ethanol or carbon dioxide supercritical fluid drying method：Ethanol supercritical is done
When dry, reaction temperature is 250～270 DEG C, and in autoclave, pressure is 8～17MPa, and drying time is 1～8h；Carbon dioxide
During supercritical drying, reaction temperature is 50～70 DEG C, and in autoclave, pressure is 8～12MPa, and outgassing rate is 5～10L/
Min, drying time is 8～15h.
Air heat treatment temperature described in preferred steps (5) is between 400～1200 DEG C；Programming rate be 2-8 DEG C/
Min, heat treatment temperature retention time is 2～5h.
Beneficial effect：
(1) process is simple, low temperature synthesizes, and energy consumption is low.Using a step sol-gel process, it is simultaneously introduced silicon source and magnesium source, and
By follow-up supercritical drying and heat treatment process, make silicon source and magnesium source can react generation point at a temperature of 400 DEG C brilliant
Shi Xiang.
(2) the material heat resistance prepared is superior, and porosity is high, and specific surface area is big, and uniformly, size is little, 1200 DEG C for granule
After processing two hours, size is only 10nm.
(3) in this method, the spinelle aerogel material of preparation is completely block, and customer service conventional oxidation magnesium aeroge becomes
The weak problem of block, this is for realizing aerogel material in catalyst carrier, high-temperature gas filter, membrance separation, sensor etc.
The application in field possesses positive meaning.
Brief description
Fig. 1 is the photo in kind of the block spinelle aerogel material of high temperature resistant low temperature synthesis that example 1 is obtained；
Fig. 2 is XRD diffraction pattern at a temperature of different heat treatment for the spinelle aeroge in example 2；Wherein in figure ◆, ● and
Represent respectively is magnesium aluminate spinel phase, boehmite phase and magnalium hydroxyl hydrate phase.
Specific embodiment
Example 1
By Magnesium dichloride hexahydrate, Aluminium chloride hexahydrate, water, ethanol according to mol ratio 1:2:80:After 30 uniform mixing, 20
DEG C temperature, uniform stirring 4h under rotating speed 400rpm, obtain the magnalium binary sol system of partial hydrolysiss.Then by expoxy propane
Pressing with Magnesium dichloride hexahydrate mol ratio is 10:1 is added in binary sol system obtained above, in 20 DEG C of temperature, rotating speed
Pour into after uniform stirring 0.1h under 400rpm in mould and react to gel, after placing 15h, add ethanol Ageing solution, in 30 DEG C of baking
Line replacement 3 times, each 24h is entered in case.Then this wet gel is carried out ethanol supercritical drying, wherein reaction temperature is 260 DEG C,
In autoclave, pressure is 8MPa, and drying time is 8h, thus obtaining spinelle aerogel precursor body.Finally by this presoma
Aeroge carries out heat treatment under the air atmosphere of Muffle furnace, and wherein calcining heat is 400 DEG C, and programming rate is 2 DEG C/min, heat
Process time is 5h, thus obtaining final spinelle aerogel material.Find through characterizing, this block spinelle airsetting glue material
The density of material is 0.08g/cm3, 800 DEG C of heat treatments after 2 hours specific surface area be 150m2/ g, crystallite dimension is 8nm.Prepared is resistance to
The photo in kind of the block spinelle aerogel material of high temperature low temperature synthesis is as shown in figure 1, it will be seen from figure 1 that the point being obtained is brilliant
Stone aeroge assumes milky although intensity is poor, but light weight, porosity height, and specific surface area is big.
Example 2
By nine nitric hydrate magnesium, ANN aluminium nitrate nonahydrate, water, ethanol according to mol ratio 1:1.5:100:After 40 uniform mixing,
Uniform stirring 1h under 40 DEG C of temperature, rotating speed 500rpm, obtains the magnalium binary sol system of partial hydrolysiss.Then will be suitable
It is 8 that formula -2,3 epoxy butane is pressed with Magnesium dichloride hexahydrate mol ratio:1 is added in binary sol system obtained above, 40
DEG C temperature, uniformly continue stirring 0.5h under rotating speed 500rpm after pour into and react in mould to gel, add acetone after placing 20h
Ageing solution, enters line replacement 4 times, each 12h in 50 DEG C of baking oven.Then this wet gel is carried out ethanol supercritical drying, its
Middle reaction temperature is 250 DEG C, and in autoclave, pressure is 10MPa, and drying time is 2h, thus before obtaining spinelle aeroge
Drive body.Finally this precursor gas gel is carried out different temperatures heat treatment under the air atmosphere of Muffle furnace, programming rate is 5
DEG C/min, heat treatment time is 2h, thus obtaining final spinelle aerogel material.Find through characterizing, this bulk point is brilliant
The density of stone aerogel material is 0.12g/cm3, 700 DEG C of heat treatments after 2 hours specific surface area be 163m2/ g, crystallite dimension is
8.5nm.XRD diffraction pattern at a temperature of different heat treatment for the obtained spinelle aeroge is as shown in Fig. 2 can from figure
Go out, for the sample after supercritical drying, comprise only magnalium hydroxyl hydrate and two kinds of crystalline phases of boehmite, and boehmite is in
Existing amorphous state, and the degree of crystallinity of magnalium hydroxyl hydrate is higher.When heat treatment temperature increases to 400 DEG C, slowly produce in structure
Give birth to Spinel, and when heat treatment temperature reaches 600 DEG C, Spinel is more obvious, when heat treatment temperature is
When 1200 DEG C, crystal formation is complete, and crystal particle scale is calculated as 10nm through Scherrer formula.
Example 3
By nine nitric hydrate magnesium, Aluminium chloride hexahydrate, water, ethanol according to mol ratio 1:3:100:After 20 uniform mixing,
Uniform stirring 4h under 35 DEG C of temperature, rotating speed 400rpm, obtains the magnalium binary sol system of partial hydrolysiss.Then by epoxy third
It is 12 that alkane is pressed with nine nitric hydrate magnesium mol ratios:1 is added in binary sol system obtained above, in 35 DEG C of temperature, turns
Pour into after uniform stirring 1h under fast 400rpm in mould and react to gel, after placing 30h, add ethanol Ageing solution, in 40 DEG C of baking
Line replacement 5 times, each 24h is entered in case.Then this wet gel is carried out carbon dioxide supercritical fluid drying, wherein reaction temperature is 50
DEG C, in autoclave, pressure is 8MPa, and outgassing rate is 5L/min, and drying time is 8h, thus obtaining spinelle aeroge
Presoma.Finally this precursor gas gel is carried out heat treatment under the air atmosphere of Muffle furnace, wherein calcining heat is 900
DEG C, programming rate is 3 DEG C/min, and heat treatment time is 3h, thus obtaining final spinelle aerogel material.Send out through characterizing
Existing, the density of this block spinelle aerogel material is 0.08g/cm3, 800 DEG C of heat treatments after 2 hours specific surface area be 134m2/
G, crystallite dimension is 9.3nm.
Example 4
By two nitric hydrate magnesium, Aluminium chloride hexahydrate, water, ethanol according to mol ratio 1:2:110:After 45 uniform mixing,
Uniform stirring 2h under 35 DEG C of temperature, rotating speed 600rpm, obtains the magnalium binary sol system of partial hydrolysiss.Then by epoxy third
It is 10 that alcohol is pressed with two nitric hydrate magnesium mol ratios:1 is added in binary sol system obtained above, in 20 DEG C of temperature, turns
Pour into after uniform stirring 0.1h under fast 600rpm in mould and react to gel, after placing 15h, add ether Ageing solution, at 30 DEG C
Line replacement 6 times, each 24h is entered in baking oven.Then this wet gel is carried out ethanol supercritical drying, wherein reaction temperature is 270
DEG C, in autoclave, pressure is 15MPa, and drying time is 5h, thus obtaining spinelle aerogel precursor body.Finally by before this
Driving bromhidrosis gel and carry out heat treatment under the air atmosphere of Muffle furnace, wherein calcining heat is 1000 DEG C, programming rate is 5 DEG C/
Min, heat treatment time is 2h, thus obtaining final spinelle aerogel material.Find through characterizing, this block spinelle gas
The density of gel rubber material is 0.13g/cm3, 1000 DEG C of heat treatments after 2 hours specific surface area be 100m2/ g, crystallite dimension is
9.6nm.
Example 5
By Magnesium dichloride hexahydrate, ANN aluminium nitrate nonahydrate, water, ethanol according to mol ratio 1:4:120:After 30 uniform mixing,
Uniform stirring 2h under 40 DEG C of temperature, rotating speed 550rpm, obtains the magnalium binary sol system of partial hydrolysiss.Then by epoxy third
It is 16 that alkane is pressed with Magnesium dichloride hexahydrate mol ratio:1 is added in binary sol system obtained above, in 40 DEG C of temperature, turns
Pour into after uniform stirring 0.2h under fast 550rpm in mould and react to gel, after placing 20h, add n-amyl alcohol Ageing solution, at 45 DEG C
Baking oven in enter line replacement 5 times, each 24h.Then this wet gel is carried out carbon dioxide supercritical fluid drying, wherein reaction temperature
For 70 DEG C, in autoclave, pressure is 12MPa, and outgassing rate is 10L/min, and drying time is 15h, thus obtaining spinelle
Aerogel precursor body.Finally this precursor gas gel is carried out heat treatment, wherein calcining heat under the air atmosphere of Muffle furnace
For 1200 DEG C, programming rate is 8 DEG C/min, and heat treatment time is 5h, thus obtaining final spinelle aerogel material.Through
Characterize and find, the density of this block spinelle aerogel material is 0.25g/cm3, 1200 DEG C of heat treatments specific surface area after 2 hours
For 81m2/ g, crystallite dimension is 12nm.
Claims (8)
1. the preparation method of high temperature resistant low temperature synthesis bulk spinelle aerogel material, it comprises the following steps that：
(1), after magnesium source, silicon source, water, ethanol uniformly being mixed, after uniform stirring at a temperature of 20～50 DEG C, obtain hydrolysis
Magnalium binary sol system；
(2) epoxide is added in the binary sol system obtain in step (1), uniformly stirs at a temperature of 20～40 DEG C
Mix to pour into and react in mould to gel, place 15～30h；
(3) Ageing solution will be added in step (2), enter line replacement 3～6 times, 12～24h every time in 30～60 DEG C of baking oven；
(4) wet gel obtaining in step (3) is carried out supercritical drying process, obtain magnesium aluminate spinel aerogel precursor body；
(5) composite aerogel obtaining in step (4) is carried out air heat treatment under the air atmosphere of Muffle furnace, finally give
Spinelle aeroge；
Wherein：Magnesium source in step (1), silicon source, water, ethanol are according to 1：(1～4)：(70～120)：The mol ratio of (15～45)
Uniformly mix；Epoxide in step (2) and magnesium source are according to mol ratio (8～16)：1 is mixed.
2. preparation method according to claim 1 is it is characterised in that the silicon source described in step (1) is six chloride hydrate
One or more of aluminum, ANN aluminium nitrate nonahydrate, aluminium secondary butylate or aluminum isopropylate..
3. preparation method according to claim 1 is it is characterised in that the magnesium source described in step (1) is six chloride hydrate
One or more of magnesium, nine nitric hydrate magnesium, two nitric hydrate magnesium, bitter salt or monohydrate acid magnesium.
4. preparation method according to claim 1 is it is characterised in that the epoxide described in step (2) is epoxy third
One or more of alkane, cis -2,3 epoxy butanes, oxetanes or epoxy prapanol.
5. preparation method according to claim 1 is it is characterised in that mixing speed in step (1) is 400～600rpm,
Mixing time is 0.5～4h；Mixing speed in step (2) is 400～600rpm, and mixing time is 0.1～1h；Step (2)
In displacement number of times be 3～6 times, each time swap be 12～24h.
6. preparation method according to claim 1 it is characterised in that the Ageing solution described in step (3) be ethanol, methanol,
One or more of acetone, ether, n-amyl alcohol or isopropanol.
7. preparation method according to claim 1 is it is characterised in that the drying meanss described in step (5) are ethanol or two
Carbonoxide supercritical drying：During ethanol supercritical drying, reaction temperature is 250～270 DEG C, and in autoclave, pressure is 8
～17MPa, drying time is 1～8h；During carbon dioxide supercritical fluid drying, reaction temperature is 50～70 DEG C, in autoclave
Pressure is 8～12MPa, and outgassing rate is 5～10L/min, and drying time is 8～15h.
8. preparation method according to claim 1 is it is characterised in that the air heat treatment temperature described in step (5) exists
Between 400～1200 DEG C；Programming rate is 2-8 DEG C/min, and heat treatment temperature retention time is 2～5h.
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